Turnbull{3 s blue single bath mineral dyeing process (ferri-zirc) for cellulosic textiles

ABSTRACT

Certain inhibited reducing agents are combined in a single bath with a ferric salt and an alkali metal ferricyanide, which is activated by heat decomposition of the inhibited reducers, to cause reduction of the ferric salt to the ferrous state on the cellulosic, in contact with the ferricyanide, thereby producing Turnbull&#39;&#39;s Blue in the cellulosic textile. A zirconium salt is used in the bath to lock the dye to the cellulosic. The resulting uniform pure blue mineral dyeing of cellulose by this single bath process has been defined as the FERRI-ZIRC BLUE PROCESS.

United States Patent [191 Conner 1 TURNBULLS BLUE SINGLE BATH MINERALDYEING PROCESS (FERRl-ZIRC) FOR CELLULOSIC TEXTILES [75] Inventor:Charles James Conner, New

Orleans, La.

[73] Assignee: The United States of America as represented by theSecretary of Agriculture, Washington, DC.

[22] Filed: Oct. 10, 1973 [21] Appl. No.: 404,974

[52] US. Cl 8/52; 8/17 [51] Int. Cl D06p 3/60 [58] Field of Search 8/52,17, 3O

[56] References Cited UNITED STATES PATENTS 1,661,606 3/1928 Escaich8/52 1,686,540 10/1928 White 8/52 2,214,845 9/1940 Wells 8/52 2,923,5922/1960 Crosland 8/52 3,671,178 6/1972 Conner 8/52 3,702,753 11/1972Conner.... 8/52 3,705,004 12/1972 C0nner.... 8/52 3,768,965 10/1973Conner.... 8/52 3,779,702 12/1973 Conner 8/52 July 22, 1975 Conner 8/522/1974 2/1974 Conner OTHER PUBLICATIONS American Dyestuff Reporter,March 1974, pp. 37-45. Textile Research Journal, April 1964, pp.347-357. Textile Research Journal, February 1967, pp. 94-102. One-BathZirchrome Chloride Fungicide and Dye by C. J. Conner, et al.

Primary ExaminerBenjamin R. Padgett Assistant ExaminerD. P. WalshAttorney, Agent, or FirmM. Howard Silverstein; Max D. Hensley [57]ABSTRACT Certain inhibited reducing agents are combined in a single bathwith a ferric salt and an alkali metal ferri- 8 Claims, No DrawingsTURNBULLS BLUE SINGLE BATH MINERAL DYEING PROCESS (FERRI-ZIRC) FORCELLULOSIC TEXTILES A non-exclusive, irrevocable, royalty-free licensein the invention herein described throughout the worid for all purposesof the United States Government, with the power to grant sublicenses forsuch purposes, is hereby granted to the Government of the United Statesof America.

This invention relates to mineral dyeing of cellulosic textiles. Morespecifically, this invention relates to a single-bath textile dyeingprocess which utilizes a ferric salt, and ammonium sulphite of ammoniumoxalate as an inhibited reducing agent, which are combined withoutreaction with an alkali metal ferricyanide and zirconyl ammoniumcarbonate to produce a stable single bath solution. The solution thusprepared remains clear as long as it remains alkaline due to thepresence of ammonium ions. When the prescribed conditions are adhered toa Turnbulls Blue coloration is imparted to cellulosic textiles. Thefinished product contains the blue coloration combined with zirconiafrom heat decomposition of the zirconyl ammonium carbonate, causing theTurnbulls Blue-zirconia deposit to lock onto the cellulosic textile,thus making the blue pigment significantly more resistant to alkalisthan it would be if the zirconyl ammonium carbonate were not included inthe formulation.

The main object of this invention is to provide a single-bath system fordyeing Turnbulls Blue color shades by a simple pad (wetting andsqueezing out excess bath), dry and cure procedure, followed by wash anddry to remove byproducts.

A second object of this invention is to provide an attractive andappealing color shade for the textile dyer, by shorter processing andrequiring less mill equipment.

A third object of this invention is to provide a singlebath system forTurnbulls Blue mineral dyeing that can be finished with aparaffin-ammonium stearate wax, requiring no after-rinse with aluminumformo-acetate to neutralize the residual stearic acid. The hydrouszirconia in the invention dyeing reacts with and neutralizes the stearicacid, without an added step.

The utility of this invention, therefore, is obviously in the field ofmineral dyeings of cellulosic textiles to obtain attractive and specificblue color shades in finished goods such as curtains, umbrellas, tents,sails, awnings, canvas shoes, upholstery, etc.

The prior art teaches that water-soluble ferrous salts react with watersoluble alkali metal ferricyanides to produce an insoluble blue dyepigment of ferrous ferricyanide known as Turnbulls Blue. It has alsobeen known from the prior art that cellulosics can be wetted with aferrous salt, and then with a solution of alkali metal ferricyanide,using two separate baths, to produce ferrous ferricyanide by doubledecomposition.

Now, this writer has unexpectedly discovered what is disclosed in theprocess of this invention. The present invention provides a uniquesingle-bath system where a ferric salt and ammonia inhibited reducingagents; i.e., ammonium. oxalate and ammonium sulfite, are combinedtogether without reaction-with an alkali metal ferricyanide and zirconylammonium carbonate-to produce a stable single bath, clear, system aslong as it remains alkaline from the presence of ammonium ions. In thisstate it may be applied to cellulosic textiles. When the wet impregnatedtextile is heated up to about from l50 to 160C. the ammonium salts aredecomposed, ammonia leaves the system, and the oxalate and sulfite ionsremaining, are capable of reducing the ferric salt to the ferrous state,when it reacts with the ferricyanide in the cellulosic textile, toproduce ferrous ferricyanide (Turnbulls Blue). During the same heat curethe zirconyl ammonium carbonate decomposes to liberate ammonia andcarbon dioxide and produce hydrous zirconia, which is deposited as alake with the Turnbulls Blue dye pigment. Beautiful pure blue mineraldyeings are produced in the cellulose by simply wetting and heating thewetted cellulosic to develop the dye.

EQUATIONS PERTINENT TO THIS INVENTION ferrous ferricyanide Blue *Rrepresents either sodium or potassium.

Fe; [Fe(CN) .ZrO .2H O Turnbulls Blue-zirconia mineral dye SUMMARY OFTHE INVENTION In brief the present invention can best be described as aplurality of mineral dye baths as well as a mineral dyeing process forcellulosic textiles. One of the preferred embodiments would be describedas a dye bath for imparting to cellulosic textiles adurable-to-waterwashing Turnbulls Blue coloration, the said dye bathcontaining.

about from 1 to 5 parts by weight of sodium or potassium ferricyanide,

about from 2 to 5 parts by weight of ammonium oxalate monohydrate,

about from 1 to 5 parts by weight of ferric sulphate,

about from 5 to 10 parts by weight of zirconyl ammonium carbonatesolution (aqueous 10 percent ZI'OQ), and

about 60 to parts by weight of water.

Another of the preferred embodiments of this invention would bedescribed as a mineral dyeing process to impart durable-to-water-washingTurnbulls Blue coloration to cellulosic textiles, the processcomprising.

a. impregnating a cellulosic textile with an aqueous solutioncontaining. about from 1 to 5 parts by weight of potassium ferricyanide,about from 2 to 5 parts by weight of ammonium oxalate monohydrate, aboutfrom 1 to 5 parts by weight of ferric sulphate,

about from to parts by weight of ammonium sulphite monohydrate,

about from 1 to 5 parts by weight of monoethanolamine, and

about from 5 to 10 parts by weight of zirconyl ammonium carbonatesolution (aqeuous 10 percent 02);

b. removing the excess solution to obtain a wet pickup of about 70-80percent,

c. drying. the wet impregnated textile for about 2 minutes at about 120to 130C., and

d. curing the textile for about 2 minutes at about from 150 to 155C.

The following examples are provided to illustrate the preferredembodiments of the invention, and should not be construed as limitingthe invention in any manner whatever. The various formulations andtechniques were employed with paper, wood, and other textiles havingpartial quantities of cellulose.

EXAMPLE 1 5 Grams of potassium ferricyanide, grams of water and 2 gramsof ferric sulphate were dissolved together in 43 grams of water(distilled). To this was added 10 grams of ammonium sulphite(monohydrate) crystals. Upon stirring, a clear brown colored bathresulted. No Turnbulls Blue precipitated, and the sulfite reducer wasinhibited by the ammonium (alkaline) ion. This bath was capable ofdyeing a pure blue by heat (150C.) decomposition on a cellulosic.

EXAMPLE 4 The following formulation utilizes both ammonium oxalate andammonium sulfite for increased bath alka- 5 linity and stability:

grams distilled water grams distilled water grams ferric sulphate gramsammonium oxalate grams ammonium sulfite (monohydrate) gramsmonoethanolamine grams Clear Greenish-Black Bath 2 PPPPP!" 0 000000 Theaddition of a small amount of monoethanolamine gives an increasedalkaline stability and bath stability.

EXAMPLE 5 EXAMPLE 6 The incorporation of zirconyl ammonium carbonate (10percent ZrO into Example 6, produces a brighter pure blue color shadethrough lake" formation of the Turnbulls Blue with zirconia. Thefollowing formation variations were prepared and successfully evaluated:

to 5.00 grams Sodium or Potassium Ferricyanide Crystals to 85.00 gramsWater (distilled or soft) to 5.00 grams Ammonium Oxalate Crystals(monohydrate) to 5.00 grams Ferric Sulphate (Fe (SO.,) H O) to 1000grams Zirconyl Ammonium Carbonate Solution (10% ZrO to 10.00 gramsAmmonium Sulfite Crystals (monohydrate) to 5.00 grams MonoethanolamineEXAMPLE 2 EXAMPLE 3 One gram of potassium ferricyanide, 1 gram of ferricsulphate, and 1 gram of ammonium oxalate were dissolved together in 27grams of distilled water. A greenish-yellow single bath resulted, allingredients being solgrams of Clear Greenish-Black Single Bath(Ferri-Zirc) uble. On wetting a piece of scoured duck (2X4 inches) withthe bath and then heating it to 150C. for 2 minutes, a deposit ofTurnbulls Blue was produced, dyeing the fabric pure deep Turnbulls Blue,and showing ammonium oxalate to be a suitable inhibited reducer in thebath. Due to lack of sufficient ammonium ion alkalinity, the bathstability was poor, and some blue precipitations occurred in the bathafter 10 minutes. (5993-121) EXAMPLE 7 All of the above bath variationscould be used successfully to produce single bath Turnbulls Blue colorshades with heat curings at l50-155C for l to 3 minutes, using scouredduck or paper.

EXAMPLE 8 The following bath formulation gave excellent color shades, onduck, and showed a bath stability of 10 hours: (6519-82) 3.00 gramsPotassium Ferricyanide Crystals 70.00 grams Water 3.00 grams Ammoniumoxalate 3.00 grams Ferric Sulphate 10.00 grams Zirconyl AmmoniumCarbonate Solution (10% ZrO 9.00 grams Ammonium Sulfite (monohydrate)2.00 grams monoethanolamine EXAMPLE 9 Samples of scoured duck werewetted with the bath 5 from Example 8 and oven dried at C. for 2minutes, followed by oven curing at 150C. for 2 minutes. Excellentresults were obtained. Other samples were dried at C. for 1 minute,followed by oven curing at 155C. for 1 minute. Excellent results wereagain ob tained. Evaluations indicate that predrying produces a uniformdeposit ofbath solids and reaching a temperature of 150C. or higher isonly required to effect decomposition of all ammonium salts.

EXAMPLE l The amount of monoethanolamine in Example 8, was

varied'up to 5 grams, and the bath stability observed.

With 5 grams of this amine stabilizer, the life of the bath wasincreased to 48 hours.

EX MPLE 1 1 The incorporation of zirconyl ammonium carbonate in the dyealso results in a Turnbulls Blue zirconia dyeing on cellulosics, whichis much more resistant to alka line water washing than dyeing from thedye bath with out zirconyl ammonium carbonate. Two baths were preparedas follows:

gram Potassium or Sodium Ferricyanide gram Water (soft or distilled)grams Ammonium Oxalate grams Ferric Sulphate grams Zirconyl AmmoniumCarbonate ZrO grams ammonium Sulphite grams Monocthanolamine grams BathA (with Zr) gram Potassium or Sodium Ferryanide gram Water (soft ordistilled) gram Ammonium Oxalate gram Ferric Sulphate gram AmminiumSulphate gram Monocthanolamine gram Bath 8 (No Zr) EXAMPLE 12 The fabricsample A from Example 1 l after cure and wash, was wetted with a 7percent paraffin emulsion (paraffimammonium stearate type), squeezedfree of excess liquid, and oven dried at ll C. for 2 minutes, followedby raising the temperature to 150C. for 1 minute. The cooled paraffinfinished sample was deep blue in color, and water repellent (spray rated90-100).

1 claim:

1. A mineral dyeing process for imparting a Turnbulls Blue coloration tocellulosic textiles, the process consisting of impregnating a cellulosictextile with an aqueous solution containing an inhibited reducing agent,ferric salt, and alkali metal ferricyanide, and zirconyl ammoniumcarbonate, then curing the impregnated cellulosic textile.

2. A mineral dyeing process to impart durable-towater washing TurnbullsBlue coloration to cellulosic textiles, the process comprising.

a. impregnating a cellulosic textile with an aqueous solutioncontaining.

about from 1 to 5 parts by weight of sodium ferricyanide,

about from 2 to 5 parts by weight of ammonium oxalate monohydrate,

about from 1 to 5 parts by weight of ferric sulphate,

about from 1 to 10 parts by weight of ammonium sulphite monohydrate,

about from 1 to 5 parts by weight of monoethanol' amine, and

about from 5 to 10 parts by weight of zirconyl ammonium carbonatesolution (aqueous 10 percent Z);

b. removing the excess solution to obtain a wet pickup of about -80percent,

c. drying the wet impregnated textile for about 2 minutes at about to C,and

d. curing the textile for about 2 minutes at about from to C.

3. A mineral dyeing process to impart durable towater washing TurnbullsBlue coloration to cellulosic textiles, the process comprising.

a. impregnating a cellulosic textile with an aqueous solutioncontaining.

about from l to 5 parts by weight of potassium ferricyanide,

about from 2 to 5 parts by weight of ammonium oxalate monohydrate,

about from 1 to 5 parts by weight of ferric sulphate,

about from 5 to 10 parts by weight of ammonium sulphite monohydrate,

about from 1 to 5 parts by weight of monoethanolamine, and

about from 5 to 10 parts by weight of zirconyl ammonium carbonatesolution (aqueous 10 percent ZrO b. removing the excess solution toobtain a wet pickup of about 70-80 percent,

c. drying the wet impregnated textile for about 2 minutes at about 120to 130C, and

d. curing the textile for about 2 minutes at about from 150 to 155C.

4. A dye bath for imparting to cellulosic textiles adurable-to-water-washing Turnbulls Blue coloration, the said dye bathcontaining.

about from 1 to 5 parts by weight of sodium ferricyanide,

about from 2 to 5 parts by weight of ammonium oxalate monohydrate,

about from 1 to 5 parts by weight of ferric sulphate,

about from 5 to 10 parts by weight of ammonium sulphite monohydrate,

about from 1 to 5 parts by weight of monoethanolamine,

about from 50 to 10 parts by weight of zirconyl ammonium carbonatesolution (aqueous 10 percent ZrO and about from 60 to 85 parts by weightof water.

5. A dye bath for imparting to cellulosic textiles adurable'to-water-washing Turnbulls Blue coloration, the said dye bathcontaining.

about from 1 to 5 parts by weight of potassium ferricyanide,

7 8 about from 2 to parts by weight of ammonium oxa- 7. A dye bath forimparting to cellulosic textiles a late monohydrate, Turnbulls Bluecoloration, the dye bath containing. about from 1 to 5 parts by weightof ferric sulphate, about from 5 to parts by weight of ammonium sul- 1part b i h f potassium fe i id Phite monohydrate, 5 1 part by weight offerric sulphate, about from 1 to 5 parts by weight of monoethanol- 1part by weight of ammonium oxalate, and

amme 27 parts by weight of water to give a greenish-- about from 5 to 10parts by weight of zirconyl ammonium carbonate solution (aqueous 10percent ZrO and about from 60 to 85 parts by weight of water. 6. A dyebath for imparting to cellulosic textiles a Turnbulls Blue coloration,the dye bath containing.

yellow solution. 8. A dye bath for imparting to cellulosic textiles aTumbulls Blue coloration, the dye bath containing.

3 parts by weight of sodium ferricyanide, 3 parts by weight of ferricsulphate, 3 parts by weight of ammonium oxalate,

5 parts by weight of potassium ferricyanide, 2 parts by weight of ferricsulphate, 9 parts by weight of ammonium sulfite monohydrate, 10 parts byweight of ammonium sulphite monohy- 2 Parts y weight ofmonoethaflolamine, and

d w, d 80 parts by weight of water to give a clear greenparts by weightof water to give a clear brown ish-black solution.

solution. 20

1. A MINERAL DYEING PROCESS FOR IMPARTING A TURNBULLS BLUE COLORATION TOCELLULOSIC TEXTILES THE PROCESS CONSISTING OF IMPREGNATING A CELLULOSICTEXTILE WITH AN AQUEOUS SOLUTION CONTAINING AN INHIBITED REDUCING AGENTFERRIC SALT AND ALKALI METAL FERRICYANIDE AND ZIRCONYL AMMONIUMCARBONATE THEN CURING THE IMPREGNATED CELLULOSIC TEXTILE.
 2. A mineraldyeing process to impart durable-to-water washing Turnbull''s Bluecoloration to cellulosic textiles, the process comprising. . . a.impregnating a cellulosic textile with an aqueous solution containing. .. about from 1 to 5 parts by weight of sodium ferricyanide, about from 2to 5 parts by weight of ammonium oxalate monohydrate, about from 1 to 5parts by weight of ferric sulphate, about from 1 to 10 parts by weightof ammonium sulphite monohydrate, about from 1 to 5 parts by weight ofmonoethanolamine, and about from 5 to 10 parts by weight of zirconylammonium carbonate solution (aqueous 10 percent ZrO2); b. removing theexcess solution to obtain a wet pickup of about 70-80 percent, c. dryingthe wet impregnated textile for about 2 minutes at about 120* to 130*C.,and d. curing the textile for about 2 minutes at about from 150* to155*C.
 3. A mineral dyeing process to impart durable-to-water washingTurnbull''s Blue coloration to cellulosic textiles, the processcomprising. . . a. impregnating a cellulosic textile with an aqueoussolution containing. . . about from 1 to 5 parts by weight of potassiumferricyanide, about from 2 to 5 parts by weight of ammonium oxalatemonohydrate, about from 1 to 5 parts by weight of ferric sulphate, aboutfrom 5 to 10 parts by weight of ammonium sulphite monohydrate, aboutfrom 1 to 5 parts by weight of monoethanolamine, and about from 5 to 10parts by weight of zirconyl ammonium carbonate solution (aqueous 10percent ZrO2); b. removing the excess solution to obtain a wet pickup ofabout 70-80 percent, c. drying the wet impregnated textile for about 2minutes at about 120* to 130*C., and d. curing the textile for about 2minutes at about from 150* to 155*C.
 4. A dye bath for imparting tocellulosic textiles a durable-to-water-washing Turnbull''s Bluecoloration, the said dye bath containing. . . about from 1 to 5 parts byweight of sodium ferricyanide, about from 2 to 5 parts by weight ofammonium oxalate monohydrate, about from 1 to 5 parts by weight offerric sulphate, about from 5 to 10 parts by weight of ammonium sulphitemonohydrate, about from 1 to 5 parts by weight of monoethanolamine,about from 50 to 10 parts by weight of zirconyl ammonium carbonatesolution (aqueous 10 percent ZrO2), and about from 60 to 85 parts byweight of water.
 5. A dye bath for imparting to cellulosic textiles adurable-to-water-washing Turnbull''s Blue coloration, the said dye bathcontaining. . . about from 1 to 5 parts by weight of potassiumferricyanide, about from 2 to 5 parts by weight of ammonium oxalatemonohydrate, about from 1 to 5 parts by weight of ferric sulphate, aboutfrom 5 to 10 parts by weight of ammonium sulphite monohydrate, aboutfrom 1 to 5 parts by weight of monoethanolamine, about from 5 to 10parts by weight of zirconyl ammonium carbonate solution (aqueous 10percent ZrO2), and about from 60 to 85 parts by weight of water.
 6. Adye bath for imparting to cellulosic textiles a Turnbull''s Bluecoloration, the dye bath containing. . . 5 parts by weight of potassiumferricyanide, 2 parts by weight of ferric sulphate, 10 parts by weightof ammonium sulphite monohydrate, and 20 parts by weight of water . . .to give a clear brown solution.
 7. A dye bath for imparting tocellulosic textiles a Turnbull''s Blue coloration, the dye bathcontaining. . . 1 part by weight of potassium ferricyanide, 1 part byweight of ferric sulphate, 1 part by weight of ammonium oxalate, and 27parts by weight of water . . . to give a greenish-yellow solution.
 8. Adye bath for imparting to cellulosic textiles a Turnbull''s Bluecoloration, the dye bath containing. . . 3 parts by weight of sodiumferricyanide, 3 parts by weight of ferric sulphate, 3 parts by weight ofammonium oxalate, 9 parts by weight of ammonium sulfite monohydrate, 2parts by weight of monoethanolamine, and 80 parts by weight of water . .. to give a clear greenish-black solution.